JP6817291B2 - Ionomer laminated sheet and its manufacturing method and laminated body - Google Patents

Description

The present invention relates to a laminated sheet including a resin layer containing a methacrylic resin and a resin layer containing an ionomer, a method for producing the same, and a laminated body.

An ion-neutralized derivative of a copolymer of α-olefin and α, β-unsaturated carboxylic acid or α, β-unsaturated dicarboxylic acid anhydride (hereinafter, may be simply abbreviated as “ionomer”) is used. It has excellent toughness, impact resilience, cold resistance, abrasion resistance, transparency, and thermal adhesion. Such ionomers are widely used in applications such as golf ball cover materials, packaging materials, steel wire coating materials, and glass interlayer films, which are used by adhering to a base material.

Adhesion between the base material and the ionomer is mainly a hydrogen bond between the carboxyl group in the ionomer molecule and the polar group existing in the base material. Therefore, ionomers exhibit particularly good adhesion to metals, paper, polar polymers such as polyamide, and the like. In addition, since ionomer has many non-polar ethylene chains in the molecule, it exhibits good adhesiveness to non-polar substrates such as polyolefin. However, ionomers are difficult to adhere to polymers with relatively weak polarity, such as (meth) acrylic resins, and thus have a limited range of applications. As used herein, "(meth) acrylic" refers to acrylic or methacrylic.

Patent Document 1 discloses a method of adhering a polyolefin substrate and a polar polymer via a bonding layer made of a segmented polymer having a segment of a non-polar polyolefin and a polar segment made of an alkyl methacrylate (claim). 1). Polymethylmethacrylate is mentioned as the polar polymer (claim 6).

Patent Document 2 describes a (meth) acrylic weight via an adhesive layer made of a modified olefin polymer containing at least one functional group selected from a carboxyl group, an acid anhydride group, a hydroxyl group, and a glycidyl group. A method of laminating a coalescence and an olefin polymer is disclosed (claim 1, paragraph 0007).

In Patent Document 3, a laminated sheet in which a (meth) acrylic resin sheet is laminated on a polyolefin-based resin base material sheet via an adhesive layer such as an epoxy-based, urethane-based, vinyl acetate-based, silicon-based, or chloroprene-based sheet. (Cosmetic sheet) is disclosed (claim 1, paragraph 0031).

Patent Document 4 describes an ethylene-based copolymer obtained by polymerizing ethylene with at least one compound selected from unsaturated carboxylic acids, unsaturated carboxylic acid esters, unsaturated carboxylic acid anhydrides, and vinyl acetate. A laminated sheet in which an olefin resin layer containing the above and a (meth) acrylic resin layer are directly adhered to each other is disclosed (claim 1).

Patent Document 5 discloses a glass laminate containing a glass sheet and an ionomer intermediate layer sheet (claim 1).

Japanese Unexamined Patent Publication No. 6-256535 Japanese Unexamined Patent Publication No. 9-193189 Japanese Unexamined Patent Publication No. 2000-25168 Japanese Unexamined Patent Publication No. 2000-33676 Special Table 2012-591646

Patent Documents 1 to 4 relate to a technique for laminating a (meth) acrylic resin and an olefin resin with or without an adhesive layer. Patent Document 5 relates to a technique for laminating a glass sheet and an ionomer layer. As described above, conventionally, there has been no report on the lamination of the resin layer containing the (meth) acrylic resin and the ionomer layer. It is considered that the ion cross-linking in the ionomer molecule reduces the compatibility with the resin containing the (meth) acrylic resin and inhibits the adhesion between the resin containing the ionomer / (meth) acrylic resin. If the resin layer containing the (meth) acrylic resin and the ionomer layer can be adhered well, it is useful for various applications.

The present invention has been made in view of the above circumstances, and provides a laminated sheet provided with a resin layer containing a methacrylic resin and a resin layer containing an ionomer, and having excellent interlayer adhesiveness and adhesiveness to various substrates. The purpose is.

The present inventors have conducted extensive research and found that the adhesiveness between the phenoxy resin and the ionomer is good, and completed the present invention based on this finding. That is, the present invention provides the following laminated sheets [1] to [9], a method for producing the same, and a laminated body.
[1] A first resin layer containing a methacrylic resin, a second resin layer containing a phenoxy resin, and a third resin layer containing an ionomer are provided, and the second resin layer and the third resin layer are provided. A laminated sheet in which the resin layers are adjacent to each other.
[2] The laminated sheet of [1], wherein the second resin layer further contains a methacrylic resin.
[3] The laminated sheet of [2], wherein the second resin layer contains 50 to 99% by mass of the phenoxy resin and 50 to 1% by mass of the methacrylic resin.
[4] The laminated sheet according to any one of [1] to [3], wherein the phenoxy resin is a bisphenol A type phenoxy resin.
[5] The ionomer is an ion-neutralizing derivative of a copolymer of α-olefin and α, β-unsaturated carboxylic acid or α, β-unsaturated dicarboxylic acid anhydride [1] to [4]. One of the laminated sheets.
[6] The content of the monomer unit derived from α, β-unsaturated carboxylic acid or α, β-unsaturated dicarboxylic acid anhydride in the copolymer is 2 to 30% by mass, [5]. Laminated sheet.
[7] A laminated body in which the third resin layer of the laminated sheet according to any one of [1] to [6] is laminated adjacently on a base material.
[8] The laminate of [7], wherein the base material contains glass, metal, ceramic, wood, paper, non-woven fabric, woven fabric, leather, or resin.
[9] Any of [1] to [6], wherein at least two adjacent layers of the first resin layer, the second resin layer, and the third resin layer are laminated by melt coextrusion. Method of manufacturing laminated sheets.

Generally, the thin film molded body is classified into a flat molded body having a thickness of 5 to 250 μm (mainly classified as a “film”) and a flat molded body having a thickness of more than 250 μm (mainly classified as a “sheet”). .) Etc. can be mentioned. In the present specification, the film and the sheet are not clearly distinguished, and both are collectively referred to as a "sheet".

In the present specification, various parameters such as weight average molecular weight (Mw), melt flow rate (MFR), and glass transition temperature (Tg) are the methods in the section [Forms for Carrying Out the Invention] or [Examples]. The measured value measured in.
In the present specification, any numerical range A to B indicates a numerical range of A or more and B or less.

According to the present invention, it is possible to provide a laminated sheet provided with a resin layer containing a methacrylic resin and a resin layer containing an ionomer, and having excellent interlayer adhesiveness and adhesiveness to various base materials.

It is a schematic sectional view of the laminated sheet of one Embodiment which concerns on this invention. It is a schematic cross-sectional view of the laminated sheet of another embodiment which concerns on this invention. It is a schematic cross-sectional view of the laminated body of one Embodiment which concerns on this invention. It is a schematic cross-sectional view of the laminated body of another embodiment which concerns on this invention.

Hereinafter, the present invention will be described in detail.
"Laminated sheet"
The laminated sheet of the present invention comprises a first resin layer containing a methacrylic resin (A), a second resin layer containing a phenoxy resin (B), and a third resin layer containing an ionomer (C). A laminated sheet in which a second resin layer and a third resin layer are adjacent to each other.
The laminated sheet of the present invention can be laminated on various base materials and used as a skin material for various base materials. The laminated sheet of the present invention can be suitably used as a surface protection sheet or a design-imparting sheet for various base materials.

FIG. 1 shows a schematic cross-sectional view of a laminated sheet according to an embodiment of the present invention. In the figure, reference numeral 10X is a laminated sheet of the present embodiment, reference numeral 11 is a first resin layer containing a methacrylic resin (A), reference numeral 12 is a second resin layer containing a phenoxy resin (B), and reference numeral 13 is a reference numeral 13. The third resin layer containing the ionomer (C) is shown respectively.
The laminated sheet 10X of the illustrated example is a three-layer structure sheet including a first resin layer of one layer, a second resin layer 12 of one layer, and a third resin layer 13 of one layer. The laminated sheet of the present invention is not limited to the three-layer structure. In the laminated sheet of the present invention, the first to third resin layers may be a single layer or a plurality of layers. The laminated sheet of the present invention may contain any other layer.

FIG. 2 shows a schematic cross-sectional view of the laminated sheet of another embodiment according to the present invention. This laminated sheet is an embodiment including another resin layer. In the figure, reference numeral 10Y indicates a laminated sheet of the present embodiment, and reference numeral 14 indicates another resin layer. Reference numerals 11 to 13 are the same as those in FIG. The design of the mode including the other resin layer can be changed as appropriate.

The present inventors have found that the adhesiveness between the phenoxy resin (B) and the ionomer (C) is good. The laminated sheet of the present invention having the above configuration is excellent in interlayer adhesiveness between the second resin layer containing the phenoxy resin (B) and the third resin layer containing the ionomer (C). However, the resin layer containing the phenoxy resin (B) tends to have a relatively low glass transition temperature (hereinafter, may be abbreviated as “Tg”) and a relatively low surface hardness. By using the first resin layer containing the methacrylic resin (A), which has a higher Tg than the phenoxy resin (B) and a higher surface hardness, the heat resistance and surface hardness of the laminated sheet are improved. As a result, deterioration of the surface shape of the laminated sheet due to softening, scratches, etc. at the time of laminating on the base material can be suppressed. Since the third resin layer containing the ionomer (C) has excellent adhesiveness to various base materials, the laminated sheet of the present invention is laminated on the base material so that the third resin layer is adjacent to the base material. , It is possible to provide a laminated body having excellent adhesiveness between the base material and the laminated sheet.

(First resin layer)
<Methacrylic resin (A)>
The first resin layer contains one or more methacrylic resins (A). As the content of the methacrylic resin (A) increases, the Tg of the first resin layer increases, the heat resistance tends to improve, and the surface hardness tends to increase. The content of the methacrylic resin (A) in the first resin layer is not particularly limited, and since the first resin layer is excellent in heat resistance and surface hardness, it is preferably 50 to 80% by mass, more preferably 70. ~ 80% by mass.

The methacrylic resin (A) is polymethyl methacrylate (PMMA), which is a copolymer of methyl methacrylate (hereinafter, may be abbreviated as "MMA"), or MMA and one or two other types. It is a copolymer with the above monomer.
The content of the MMA monomer unit in the methacrylic resin (A) is not particularly limited, and since the heat resistance of the first resin layer is excellent, it is preferably 80% by mass or more, more preferably 90% by mass or more. It is more preferably 95% by mass or more, particularly preferably 99% by mass or more, and most preferably 100% by mass.

The content of the MMA monomer unit in the methacrylic resin (A) is determined by purifying the methacrylic resin (A) by reprecipitation in methanol, and then pyrolyzing and volatile components using pyrolysis gas chromatography. Separation can be performed and it can be calculated from the ratio of the peak areas of MMA and the copolymerization component.

The methacrylic resin (A) can contain one or more monomer units other than the MMA monomer unit. Examples of the monomer copolymerizable with MMA include methacrylic acid esters other than MMA. Examples of methacrylic acid esters other than MMA include alkyl methacrylates such as ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate; 1-methyl methacrylate. Examples thereof include a methacrylic acid cycloalkyl ester such as cyclopentyl; a methacrylic acid aryl ester such as phenyl methacrylate; and a methacrylic acid aralkyl ester such as benzyl methacrylate.

Examples of the monomer other than the methacrylic acid ester copolymerizable with MMA include methyl acrylate (hereinafter, may be abbreviated as "MA"), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and acrylic. Acrylic acid esters such as n-butyl acid, isobutyl acrylate, and tert-butyl acrylate can be mentioned.

The weight average molecular weight of the methacrylic resin (A) (hereinafter, may be abbreviated as “Mw”) is not particularly limited, and is preferably 40,000 to 500,000, more preferably 60,000 to 300,000. , Particularly preferably 80,000 to 200,000. When Mw is 40,000 or more, the first resin layer has excellent mechanical strength. When Mw is 500,000 or less, the first resin layer has excellent moldability.

The melt flow rate of the methacrylic resin (A) (hereinafter, may be abbreviated as "MFR") is not particularly limited, and is preferably 0.1 to 10 g / 10 minutes, more preferably 0.5 to 8 g /. It is 10 minutes, particularly preferably 1 to 5 g / 10 minutes. When the MFR is 0.1 to 10 g / 10 minutes, the first resin layer has excellent moldability. In the present specification, "MFR of methacrylic resin (A)" is a value measured under the condition of 230 ° C. and 3.8 kg load in accordance with JIS K 7210.

The glass transition temperature of the methacrylic resin (A) (hereinafter, may be abbreviated as "Tg") is not particularly limited, and is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and particularly preferably 110 ° C. or higher. is there. When the Tg is 100 ° C. or higher, the first resin layer has excellent heat resistance.

The methacrylic resin (A) can be produced by polymerizing one or more types of monomers containing MMA in the presence of a polymerization initiator. If necessary, an arbitrary component such as a chain transfer agent can be used for the polymerization. The polymerization method is not particularly limited, and examples thereof include a radical polymerization method and an anion polymerization method.
When the radical polymerization method is used, a suspension polymerization method, a massive polymerization method, a solution polymerization method, or an emulsion polymerization method can be selected. In such a polymerization method, a suspension polymerization method and a bulk polymerization method are preferable from the viewpoint of productivity and thermostable decomposition. Bulk polymerization is preferably carried out by a continuous flow method.
As a method of anionic polymerization of the methacrylic resin (A), for example, a method of anionic polymerization using an organoalkali metal compound as a polymerization initiator in the presence of a mineral acid such as a salt of an alkali metal or an alkaline earth metal (special fairness). 7-25859 (see Japanese Patent Application Laid-Open No. 7-25859), a method of anionic polymerization using an organoalkali metal compound as a polymerization initiator in the presence of an organoaluminum compound (see JP-A-11-335432), and an organic rare earth metal complex as a polymerization initiator. Examples thereof include a method of anionic polymerization (see JP-A-6-93060).

The various characteristic values of the methacrylic resin (A) described in the present specification are determined by adjusting the polymerization conditions such as the polymerization temperature, the polymerization time, the type and amount of the polymerization initiator, and the type and amount of the chain transfer agent. , Can be adjusted within a preferred range.

The first resin layer may contain a polymer other than the methacrylic resin (A) as long as the effects of the present invention are not impaired. Other polymers include polyolefins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene-based ionomers; polystyrene, styrene-maleic anhydride copolymers, high-impact polystyrene, etc. Sterite resins such as AS resin, ABS resin, AES resin, AAS resin, ACS resin, and MBS resin; methyl methacrylate-styrene copolymer; polyesters such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, And polyamides such as polyamide elastomers; polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene oxide, polyimide, polyetherimide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol, ethylene-vinyl alcohol Polymers and other thermoplastic resins such as polyacetal; thermocurable resins such as phenolic resin, melamine resin, silicone resin, and epoxy resin; polyurethane; modified polyphenylene ether; silicone modified resin; acrylic core shell Examples include rubbers, acrylic block copolymers, silicone rubbers; styrene-based thermoplastic elastomers such as SEPS, SEBS, and SIS; olefin-based rubbers such as IR, EPR, and EPDM. These can be used alone or in combination of two or more. The content of the other polymer in the first resin layer is not particularly limited, and is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

The first resin layer may contain various additives, if necessary. Additives include antioxidants, heat deterioration inhibitors, UV absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes / pigments, light diffusers, and luster. Examples include erasers, impact-resistant modifiers, fillers and phosphors. The content of the additive can be appropriately set as long as the effect of the present invention is not impaired. For example, the content of the antioxidant is preferably 0.01 to 1% by mass, the content of the ultraviolet absorber is preferably 0.01 to 3% by mass, and the content of the light stabilizer is preferably 0.01 to 3% by mass. The mass%, the content of the lubricant is preferably 0.01 to 3% by mass, and the content of the dye / pigment is preferably 0.01 to 3% by mass.

An ultraviolet absorber is a compound having an ability to absorb ultraviolet rays. The ultraviolet absorber is a compound that is said to have a function of mainly converting light energy into heat energy. Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic acid esters, and formamidines. These can be used alone or in combination of two or more. Among them, benzotriazoles, triazines, and ultraviolet absorbers having a maximum molar extinction coefficient ε _max of 1200 dm ³ · mol ^-1 cm ^-1 or less at a wavelength of 380 to 450 nm are preferable.

Benzotriazoles are highly effective in suppressing deterioration of optical properties such as coloring due to exposure to ultraviolet rays, and are therefore preferable as an ultraviolet absorber used when the laminated sheet of the present invention is applied to optical applications. Examples of benzotriazoles include 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol ("trade name TINUVIN329" manufactured by BASF Japan Ltd.), 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (“TINUVIN234” manufactured by BASF Japan Ltd.), and 2,2′-methylenebis [6- (2H-benzotriazole-2-yl) -4-tert-octylphenol] (“Adecastab LA-31” manufactured by ADEKA Co., Ltd.) and the like are preferable.

Further, when it is desired to efficiently absorb a wavelength in the vicinity of 380 nm, a triazine-type ultraviolet absorber is preferably used. Examples of such an ultraviolet absorber include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (“Adecastab LA-F70” manufactured by ADEKA Co., Ltd.” ), And its analogs, hydroxyphenyltriazine-based ultraviolet absorbers (“TINUVIN 477” and “TINUVIN 460” manufactured by BASF Japan Ltd.) and the like.

An ultraviolet absorber containing a sulfur atom in the skeleton is preferable when the laminated sheet of the present invention is applied to optical applications because it can increase the refractive index of the resin composition in addition to the ultraviolet absorbing ability. Examples of the ultraviolet absorber containing a sulfur atom in the skeleton include 2- (5-octylthio-2H-benzotriazole-2-yl) -6-tert-butyl-4-methylphenol (Compound A) as benzotriazoles. , 2- (5-dodecylthio-2H-benzotriazole-2-yl) -6-tert-butyl-4-methylphenol (Compound B) and the like. In addition, as triazines, 2,4-diphenyl-6- (2-hydroxy-4-methylthiophenyl) -1,3,5-triazine (Compound C), and 2,4,6- (2-hydroxy-4). −Hexylthiophenyl) -1,3,5-triazine (Compound D) and the like can be mentioned.
An ultraviolet absorber containing a sulfur atom in the skeleton can increase the refractive index of the resin composition, but may have absorption in the visible light region having a wavelength of 380 nm or more, which causes the resin composition to be colored. Sometimes. Therefore, it is preferable to use it in combination with other ultraviolet absorbers to make the amount used appropriate.

When used in combination with an ultraviolet absorber, among the ultraviolet absorbers, benzotriazoles that do not contain sulfur atoms in the skeleton [1], triazoles that do not contain sulfur atoms in the skeleton [2], and in the skeleton When the ultraviolet absorber containing a sulfur atom is labeled as [3], for example, [1] and [2]; [1] and [3]; [2] and [3]: [1] and [2]. Examples thereof include combinations such as [3]. Further, an ultraviolet absorber that does not correspond to any of [1] to [3] may be used in combination with [4].

When an arbitrary component is contained in the first resin layer, it may be mixed with the methacrylic resin (A) or added at the time of polymerization of the methacrylic resin (A). When the first resin layer contains an arbitrary component, the Tg of the raw material resin composition of the first resin layer is not particularly limited, and from the viewpoint of heat resistance, it is preferably 98 to 120 ° C., more preferably 100 to 118 ° C. Particularly preferably, it is 102 to 115 ° C. When the first resin layer contains an optional component, when the first resin layer contains an optional component, the MFR of the raw material resin composition of the first resin layer is not particularly limited, and the moldability of the first resin layer is not particularly limited. Is preferably 1 to 20 g / 10 minutes. The lower limit of MFR is preferably 1.5 g / 10 minutes or more, and more preferably 2.0 g / 10 minutes. The upper limit of MFR is preferably 10.0 g / 10 minutes or less, more preferably 7.0 g / 10 minutes or less.

(Second resin layer)
<Phenoxy resin (B)>
The second resin layer contains one or more phenoxy resins (B). As the content of the phenoxy resin (B) in the second resin layer increases, the interlayer adhesiveness with the third resin layer containing the ionomer (C) tends to improve. However, as the content of the phenoxy resin (B) increases, the Tg of the second resin layer decreases, so that the heat resistance tends to decrease and the surface hardness tends to decrease. In the present invention, these drawbacks are eliminated by using a first resin layer containing the methacrylic resin (A).

Since the Tg of the second resin layer itself can be increased and the heat resistance can be improved, the second resin layer may contain one or more kinds of methacrylic resin (A) according to the phenoxy resin (B). preferable. The methacrylic resin (A) used for the second resin layer is any methacrylic resin that can be used for the first resin layer, and the preferable structure and physical properties are described in the above item (first resin layer). Please refer. The methacrylic resin (A) in the first resin layer and the methacrylic resin (A) in the second resin layer may be the same or non-identical.

The content of the phenoxy resin (B) in the second resin layer is not particularly limited, and since it is excellent in interlayer adhesion with the third resin layer, it is preferably 20 to 100% by mass, more preferably 50 to 50 to 100% by mass. It is 100% by mass.

When the second resin layer contains the phenoxy resin (B) and the methacrylic resin (A), the second resin layer has a second resin layer from the viewpoint of interlayer adhesion with the third resin layer and a Tg improving effect of the second resin layer. The resin layer of No. 1 preferably contains 50 to 99% by mass of the phenoxy resin (B) and 50 to 1% by mass of the methacrylic resin (A), and 50 to 80% by mass of the phenoxy resin (B) and 50. It is more preferable to contain ~ 20% by mass of the methacrylic resin (A).

The phenoxy resin (B) is a high molecular weight epoxy resin having thermoplasticity, and refers to a polyhydroxyxypolyether having a chain having a hydroxy group-containing portion and an aromatic unit. Specifically, the phenoxy resin (B) is a resin containing one or more units represented by the following formula (1). The phenoxy resin (B) preferably contains 50% by mass or more of the unit represented by the following formula (1).

In the above formula (1), X is a divalent group containing at least one benzene ring, and R is a linear or branched alkylene group having 1 to 6 carbon atoms.

X is preferably a divalent group derived from the compounds (2) to (4) represented by the following formulas. The positions of the two substituents constituting the divalent group are not particularly limited as long as they are structurally possible, but two hydrogen atoms on the benzene ring in the compounds (2) to (4) are extracted. A divalent group is preferable. In particular, a divalent group in which a total of two hydrogen atoms on different benzene rings in the compound (2) or (4) are extracted is preferable.

In the above formula (2), R ¹ is a linear or branched alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms or a cycloalkylidene group, or R ¹ having no atom. It shows a linearly bonded naphthalene structure or a biphenyl structure. R ² and R ³ are independently hydrogen atoms, straight-chain or branched-chain alkyl groups having 1 to 6 carbon atoms, and straight-chain or branched-chain alkenyl groups having 2 to 6 carbon atoms. n and m are independently integers 1 to 4.

In the above formula (3), R ⁴ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a straight-chain or branched alkenyl group having 2 to 6 carbon atoms. p is an integer of 1 to 4.

In the above formula (4), R ⁶ and R ⁷ are independently a linear or branched alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms or a cycloalkylidene group, or R ⁶ , R ⁷ shows a naphthalene structure or a biphenyl structure in which no atom is present and is directly bonded. R ⁵ and R ⁸ are independently hydrogen atoms, linear or branched alkyl groups having 1 to 6 carbon atoms, and linear or branched chain alkenyl groups having 2 to 6 carbon atoms. q and r are independently integers 1 to 4.

In the above formula (1), X may be a divalent group derived from an aromatic hydrocarbon having a tricyclic structure. Specific examples thereof include a fluorene structure and a carbazole structure.

Specific examples of the compounds (2) to (4) include divalent phenol derivatives of the aromatic compound shown in [Chemical Formula 5].

Among the units represented by the above formula (1), the unit represented by the following formula (6) is preferable.

In the above formula (6), R ⁹ is a linear or branched alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms or a cycloalkylidene group, or R ⁹ having no atom. It shows a linearly bonded naphthalene structure or a biphenyl structure. R ¹⁰ is a linear or branched alkylene group having 1 to 6 carbon atoms.

Among the units represented by the above formula (6), the unit represented by the following formula (7) is preferable.

The terminal portion of the phenoxy resin (B) preferably does not contain an epoxy group. When the phenoxy resin (B) contains a large amount of epoxy groups at the ends, the epoxy groups react with the methacrylic resin (A) to be near the interface between the first resin layer and the second resin layer or to the second resin layer. Gel defects may occur in the resin layer of.

The phenoxy resin (B) preferably contains 10 to 1000 units represented by the above formula (1), more preferably 15 to 500 units, and particularly preferably 30 to 300 units.

The Mw of the phenoxy resin (B) is not particularly limited, and is preferably 30,000 to 100,000, more preferably 40,000 to 80,000, and particularly preferably 50,000 from the viewpoint of mechanical strength and heat resistance. ~ 60,000.
The MFR of the phenoxy resin (B) is not particularly limited, and the moldability of the second resin layer is improved. Therefore, it is preferably 2 to 40 g / 10 minutes, more preferably 5 to 30 g / 10 minutes, and particularly preferably. Is 10 to 25 g / 10 minutes.
In the present specification, "MFR of phenoxy resin (B)" is a value measured under the condition of 230 ° C. and 3.8 kg load in accordance with JIS K 7210.
The Tg of the phenoxy-based resin (B) is not particularly limited, and since the heat resistance of the second resin layer is excellent, it is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and particularly preferably 95 ° C. or higher.

The phenoxy resin (B) may be either a bisphenol A type or a bisphenol A / F copolymer type, has good compatibility with the methacrylic resin (A), and has good interlayer adhesion with the first resin layer and a second resin layer. Bisphenol A type is preferable because the transparency of the resin layer is good.

As the phenoxy resin (B), Nippon Steel & Sumikin Chemical Co., Ltd.'s Phenotote series (YP-50, YP-50S, etc.), Mitsubishi Chemical Corporation's JER series (1256, 4250, etc.), and InChem's. Commercially available products such as PKFE and PKHL can be used. The phenoxy resin (B) may be produced and used by a known method. The phenoxy resin (B) can be obtained, for example, from a condensation reaction between a divalent phenol compound and epihalohydrin, or a double addition reaction between a divalent phenol compound and a bifunctional epoxy resin. These reactions can be carried out in solution or in the absence of solvent.

When the second resin layer contains the phenoxy resin (B) and the methacrylic resin (A), examples of the method for mixing these resins include a melt mixing method and a solution mixing method. In the melt-mixing method, a single-screw or double-screw kneading extruder, an open roll, a Banbury mixer, and a melt-kneader such as a kneader are used, and if necessary, the inert gas such as nitrogen gas, argon gas, and helium gas is used. Melt kneading can be performed in a gas atmosphere. In the solution mixing method, the phenoxy resin (B) and the methacrylic resin (A) can be dissolved in an organic solvent such as toluene, tetrahydrofuran, and methyl ethyl ketone and mixed. Among these mixing methods, the melt mixing method is preferable, and the method using a single-screw or twin-screw kneading extruder is particularly preferable. The temperature at the time of mixing and kneading can be appropriately adjusted according to the melting temperature of the phenoxy resin (B) and the methacrylic resin (A) to be used, and is preferably 110 to 300 ° C.

The second resin layer may contain a polymer other than the phenoxy resin (B) and the methacrylic resin (A) and / or various additives as long as the effects of the present invention are not impaired. The types and preferable contents of the other polymers and various additives that can be used are the same as those of the first resin layer, and refer to the section (1st resin layer) above.

When the second resin layer containing the phenoxy resin (B) contains an arbitrary component, it may be mixed with the phenoxy resin (B) or added at the time of polymerization of the phenoxy resin (B). When an arbitrary component is contained in the second resin layer containing the phenoxy resin (B) and the methacrylic resin (A), it is added at the time of polymerization of the phenoxy resin (B) and / or the methacrylic resin (A). It may be added when mixing the phenoxy resin (B) and / or the methacrylic resin (A), or it may be added after mixing the phenoxy resin (B) and the methacrylic resin (A). You may.

When the second resin layer contains an arbitrary component, the Tg of the raw material resin composition of the second resin layer is not particularly limited, and from the viewpoint of heat resistance, it is preferably 98 to 120 ° C., more preferably 100 to 118 ° C. Particularly preferably, it is 102 to 115 ° C. When the second resin layer contains an arbitrary component, the MFR of the raw material resin composition of the second resin layer is not particularly limited, and the moldability of the second resin layer is improved. Therefore, 1 to 20 g is preferable. / 10 minutes. The lower limit of MFR is preferably 1.5 g / 10 minutes or more, and more preferably 2.0 g / 10 minutes. The upper limit of MFR is preferably 10.0 g / 10 minutes or less, more preferably 7.0 g / 10 minutes or less.

(Third resin layer)
<Ionomer (C)>
The third resin layer contains one or more ionomers (C). The content of ionomer (C) in the third resin layer is not particularly limited, and since the third resin layer is excellent in transparency and substrate adhesiveness, it is preferably 90% by mass or more, more preferably 95% by mass. % Or more, particularly preferably 98% by mass or more, and most preferably 100% by mass.

Ionomer (C) is a copolymer containing an α-olefin monomer unit and a monomer unit derived from α, β-ethylenic unsaturated carboxylic acid or α, β-ethylene unsaturated dicarboxylic acid anhydride. It is a polymer obtained by partially or completely neutralizing (hereinafter, may be simply referred to as "acid copolymer"). The acid copolymer may contain one or more other copolymerization units such as α, β-ethylenically unsaturated carboxylic acid ester. That is, the ionomer (C) is an acid copolymer containing an α-olefin unit and a monomer unit derived from an α, β-ethylenically unsaturated carboxylic acid or an α, β-ethylenically unsaturated dicarboxylic acid anhydride. Ion-neutralized derivatives are preferred. Neutralization of an acid copolymer is a reaction of neutralizing an anions in an acid copolymer using cations. As the cation source, an alkali metal, an alkaline earth metal, a transition metal or the like can be used.

As the α-olefin which is a raw material of the acid copolymer, an α-olefin having 2 to 10 carbon atoms is preferable. Examples of such α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene and the like. These can be used alone or in combination of two or more. Of these, ethylene is preferable.

The α, β-ethylene unsaturated carboxylic acid or α, β-ethylene unsaturated dicarboxylic acid anhydride used as the raw material of the acid copolymer is an α, β-ethylene unsaturated carboxylic acid having 3 to 8 carbon atoms. Acids or α, β-ethylenic unsaturated dicarboxylic acid anhydrides are preferred. Examples of the α, β-ethylenically unsaturated carboxylic acid or α, β-ethylenically unsaturated dicarboxylic acid anhydride include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid anhydride, fumaric acid, and monomethylmaleine. Examples include acid. These can be used alone or in combination of two or more. Of these, acrylic acid, methacrylic acid, and combinations thereof are preferable, and methacrylic acid is particularly preferable.

The content of the monomer unit derived from α, β-ethylenically unsaturated carboxylic acid or α, β-ethylenically unsaturated dicarboxylic acid anhydride in the acid copolymer is not particularly limited, and is preferably 2 to 30% by mass. , More preferably 5 to 25% by mass, and particularly preferably 18 to 24% by mass. When the content is 2% by mass or more, the adhesiveness with the base material is good, and when it is 30% by mass or less, the hardness and elasticity are good.

Acid copolymers may contain monomeric units derived from α-olefins, α, β-ethylenically unsaturated carboxylic acids, and other monomers other than α, β-ethylenically unsaturated dicarboxylic acid anhydrides. it can. Thereby, for example, the rigidity and the ease of winding of the laminated sheet can be adjusted.

Examples of other monomers used in the acid copolymer include unsaturated carboxylic acid amides and unsaturated carboxylic acid esters, and unsaturated carboxylic acid esters are preferable. Examples of unsaturated carboxylic acid esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate and acrylic acid. Isobutyl, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, octyl acrylate, octyl methacrylate, undecyl acrylate, undecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, dodecyl acrylate, dodecyl methacrylate, 2-Ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, Poly (ethylene glycol) acrylate, poly (ethylene glycol) methacrylate, poly (ethylene glycol) methyl ether acrylate, poly (ethylene glycol) methyl ether methacrylate, poly (ethylene glycol) behenyl ether acrylate, poly (ethylene glycol) behenyl ether methacrylate , Poly (ethylene glycol) 4-nonylphenyl ether acrylate, poly (ethylene glycol) 4-nonylphenyl ether methacrylate, poly (ethylene glycol) phenyl ether acrylate, poly (ethylene glycol) phenyl ether methacrylate, dimethyl maleate, diethyl maleate , Dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, vinyl acetate, vinyl propionate and the like. These can be used alone or in combination of two or more. Among them, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl methacrylate, vinyl acetate, and combinations thereof are preferable, and butyl acrylate is more preferable.
The content of monomeric units derived from α-olefins, α, β-ethylenic unsaturated carboxylic acids, and other monomers other than α, β-ethylenic unsaturated dicarboxylic acid anhydrides in the acid copolymers It is not particularly limited, and is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, particularly preferably 1% by mass or less, and most preferably 0%.

The MFR of the acid copolymer is not particularly limited, and is preferably 1 to 1000 g / 10 minutes, more preferably 20 to 900 g / 10 minutes. In the present specification, "MFR of acid copolymer" is a value measured under the conditions of 190 ° C. and 2.16 kg load according to ASTM method D1238.

As the acid copolymer, a commercially available product such as the Nuclel series manufactured by Mitsui-DuPont Polychemical Co., Ltd. can be used. Acid copolymers include US Pat. No. 3,404,134, US Pat. No. 5,028,674, US Pat. No. 6,500,888, and US Pat. No. 6,518,365. It may be polymerized and used by a known method described in the specification or the like.

The ionomer (C) is obtained by partially or completely neutralizing the acid copolymer described above by reaction with one or more bases. After the neutralization reaction, 1 to 100% of the hydrogen atoms of the α, β-ethylenically unsaturated carboxy group in the acid copolymer are preferably neutralized, and more preferably 5 to 90%. It is preferably neutralized by 10 to 60%, particularly preferably.

The ionomer (C) contains a cation as a counterion to the carboxylate anion. The cation is not particularly limited, and a monovalent, divalent, trivalent, or tetravalent or higher polyvalent metal cation is preferable. One kind or two or more kinds of metal cations can be used. Examples of the monovalent metal cation include sodium ion, potassium ion, lithium ion, silver ion, mercury ion, copper ion, and a combination thereof. Divalent metal cations include beryllium ion, magnesium ion, calcium ion, strontium ion, barium ion, copper ion, cadmium ion, mercury ion, tin ion, lead ion, iron ion, cobalt ion, nickel ion, zinc ion, etc. And combinations of these. Examples of the trivalent metal cation include aluminum ion, scandinium ion, iron ion, yttrium ion, and a combination thereof. Examples of the tetravalent or higher polyvalent metal cation include titanium ion, zirconium ion, hafnium ion, vanadium ion, tantalum ion, tangstin ion, chromium ion, cerium ion, iron ion, and a combination thereof. If the metal cation is a tetravalent or higher multivalent ion, a complexing agent such as stearate, oleate, salicylate and phenolate radicals is used as described in US Pat. No. 3,404,134. You may. Among them, monovalent or divalent metal cations are preferable, sodium ions, lithium ions, magnesium ions, zinc ions, potassium ions, and combinations thereof are more preferable, and sodium ions, zinc ions, and combinations thereof are particularly preferable.

The MFR of the ionomer (C) is not particularly limited, and the moldability of the third resin layer is improved. Therefore, it is preferably 25 g / 10 minutes or less, more preferably 20 g / 10 minutes or less, and particularly preferably 10 g / 10. Minutes or less, most preferably 5 g / 10 minutes or less. In the present specification, "MFR of ionomer (C)" is a value measured under the conditions of 190 ° C. and 2.16 kg load according to ASTM method D1238.

As the ionomer (C), commercially available products such as the Sarlin series manufactured by DuPont and the Hymilan series manufactured by Mitsui DuPont Polychemical Co., Ltd. can be used. Methods for neutralizing acid copolymers to obtain ionomers (C) are described in US Pat. Nos. 3,404,134 and US Pat. No. 6,518,365. Ionomer (C) may be synthesized and used according to these known methods.

The third resin layer may contain a polymer other than the ionomer (C) as long as the effects of the present invention are not impaired. The third resin layer may contain a methacrylic resin (A) and / or a phenoxy resin (B). The third resin layer may contain various polymers other than the methacrylic resin (A) and the phenoxy resin (B). The third resin layer may contain known additives. The types and preferable contents of various polymers and various additives other than the methacrylic resin (A) and the phenoxy resin (B) are the same as those of the first resin layer, and the above (first resin layer) See section (excluding ethylene ionomers).

(Laminated structure)
In the laminated sheet of the present invention, the first to third resin layers may be a single layer or a plurality of layers, and may have a resin layer other than the first to third resin layers. The constituent resins of the other resin layers are not particularly limited, and one or more thermoplastic resins except methacrylic resin (A), phenoxy resin (B), and ionomer (C), one or two. Examples thereof include the above thermosetting resins, one or more energy ray-curable resins, and combinations thereof.

The functions of the other resin layers are not particularly limited, and support layers that support the first to third resin layers; scratch resistant layer, antistatic layer, antifouling layer, friction reducing layer, antiglare layer, antireflection layer, It may function as various functional layers such as an adhesive layer, a heat ray absorbing layer, a sound insulating layer, and an impact strength imparting layer. The other resin layer may be singular or plural. When there are a plurality of other resin layers, the composition may be the same or non-identical.

In the laminated sheet of the present invention, the thickness of the first resin layer is not particularly limited, and is preferably 0.01 to 9.0 mm, more preferably 0.01 to 9.0 mm, from the viewpoint of scratch resistance, weather resistance, impact resistance, and the like. It is 0.05 to 5.0 mm, particularly preferably 0.02 to 3.0 mm. In the laminated sheet of the present invention, the thickness of the second resin layer is not particularly limited, and is preferably 0.01 to 9.0 mm, more preferably 0.015 to 3.0 mm, particularly from the viewpoint of interlayer adhesion. It is preferably 0.02 to 1.0 mm.
In the laminated sheet of the present invention, the thickness of the third resin layer is not particularly limited, and is preferably 0.01 to 9.0 mm from the viewpoint of penetration resistance, adhesiveness, transparency, productivity and the like. It is preferably 0.05 to 4.0 mm, particularly preferably 0.1 to 2.0 mm. The overall thickness of the laminated sheet of the present invention is not particularly limited, and is preferably 0.1 to 10.0 mm, more preferably 0.5 to 6.0 mm, particularly preferably 0.5 to 6.0 mm, from the viewpoint of producing with good productivity without poor appearance. It is 0.8.0 mm.

From the viewpoint of improving scratch resistance, the laminated sheet of the present invention preferably has one outermost surface layer of the first resin layer (1). From the viewpoint of adhesiveness to various substrates, the other outermost layer is preferably a third resin layer (3).

"Manufacturing method of laminated sheet"
The method for producing the laminated sheet of the present invention is not particularly limited, and the first to third resin layers are preferably laminated by a known multi-layer molding. Examples of the multi-layer molding include a multi-layer coextrusion molding; a multi-layer blow molding; a multi-layer press molding; a multi-color injection molding; a pasting synthetic molding method such as an insert injection molding. Multi-layer coextrusion molding is preferable from the viewpoint of productivity. In addition, in this specification, "multilayer molding" means the laminated molding of two or more layers.

The method of further laminating the other resin layers is not particularly limited, and a method of multi-layer molding the other resin layers together with the first to third resin layers by the method described above, and a method of preliminarily prepared first to third resin layers. A method of applying another fluid resin to the surface of any of the layers and drying, solidifying or curing the resin, or a method of applying an adhesive layer to the surface of any of the first to third resin layers prepared in advance. Examples thereof include a method of laminating other resin layers.

The multi-layer coextrusion molding can be carried out by a known method such as laminating by melt coextrusion, and at least two layers of the first to third resin layers adjacent to each other can be laminated by melt coextrusion. A T-die that extrudes the raw material resin (composition) of the first to third resin layers in a molten state into a sheet in a laminated state, and a T-die that pressurizes the molten sheet-like material extruded from the T-die while cooling each other. It is preferable to carry out multi-layer coextrusion molding using an apparatus including a roll unit composed of a plurality of rolls arranged adjacent to each other.

The lamination method includes a feed block method in which the raw material resin (composition) of the first to third resin layers in the molten state is laminated before the inflow of the T die, and a raw material of the first to third resin layers in the molten state. An example is a multi-manifold method in which a resin (composition) is laminated inside a T-die. Above all, the multi-manifold method is preferable from the viewpoint of improving the interfacial smoothness between each layer of the laminated sheet.

Examples of the roll constituting the roll unit include a polishing roll having a mirror-finished roll surface; a rubber roll in which rubber is wound around the surface of a metal, stainless steel, and carbon steel core; and a fine embossed pattern (unevenness pattern) on the roll surface. ), And the like. The roll on the side in contact with the first resin layer forming the outermost surface layer is preferably a polishing roll for the purpose of imparting mirrorability. The roll on the side in contact with the third resin layer forming the other outermost layer is preferably a rubber roll or an embossed roll from the viewpoint of peelability from the roll.

Examples of the polishing roll include a metal roll and an elastic roll provided with a metal thin film on the outer peripheral portion (hereinafter, may be abbreviated as "metal elastic roll"). The metal roll is not particularly limited as long as it has high rigidity, and examples thereof include a drilled roll and a spiral roll. The surface state of the metal roll is not particularly limited, and may be a mirror surface, or may have a pattern or unevenness. The metal elastic roll is, for example, a substantially columnar rotatable shaft roll, a cylindrical metal thin film arranged so as to cover the outer peripheral surface of the shaft roll and in contact with a sheet-like object, and these shaft rolls and metal. It consists of a fluid enclosed between thin films, which makes the metal elastic roll elastic. The shaft roll is not particularly limited, and is made of, for example, stainless steel. The metal thin film is made of, for example, stainless steel, and its thickness is preferably about 2 to 5 mm. The metal thin film preferably has flexibility, flexibility, and the like, and preferably has a seamless structure without weld joints. A metal elastic roll provided with such a metal thin film has excellent durability, and can be handled in the same manner as a normal mirror surface roll by mirroring the metal thin film, and if a pattern or unevenness is imparted to the metal thin film. It is easy to use because it becomes a roll that can transfer the shape.

Examples of the rubber roll include a silicone rubber roll, a fluorine rubber roll, a nitrile butadiene rubber roll, a styrene butadiene rubber, and a rubber roll mixed with sand to improve releasability. The rubber roll used is not particularly limited, and a silicone rubber roll is preferable from the viewpoint of heat resistance. A known processing method can be used for surface finishing of the silicone rubber roll.

As the embossed roll, for example, the surface of the metal roll is blasted with a grinding material such as aluminum oxide and silicon oxide, and then wrapping is performed using vertical grinding or the like to reduce the excessive peak on the surface. An embossed roll in which a fine embossed pattern (unevenness pattern) is provided on the roll surface can be mentioned. Another example is an embossed roll in which a fine embossed pattern (unevenness pattern) is imparted to the surface of the roll by transferring the embossed pattern (unevenness pattern) to the surface of the metal roll using an engraving mill (mother mill). Further, an embossed roll in which a fine embossed pattern (concave and convex pattern) is imparted to the roll surface by etching (eching) can be mentioned. It is preferable to perform a mold release treatment on the surface of the embossed roll. Examples of the mold release treatment include silicone treatment, Teflon (registered trademark) treatment, and plasma treatment.

The raw material resin (composition) for each layer of the laminated sheet is preferably filtered by a filter before and / or during multi-layer molding. By multi-layer molding using the filter-filtered raw material resin (composition), a laminated sheet having few defects caused by foreign substances and gel can be obtained. The material of the filter used is not particularly limited, and is appropriately selected according to the operating temperature, viscosity, filtration accuracy, etc., for example, a non-woven fabric made of polypropylene, polyester, rayon, cotton, glass fiber, etc .; phenolic resin impregnated cellulose Films; metal fiber non-woven fabric sintered films; metal powder sintered films; wire meshes; and combinations thereof can be used. Above all, from the viewpoint of heat resistance and durability, it is preferable to use a plurality of laminated metal fiber non-woven fabric sintered films. The opening diameter of the filter is not particularly limited, and is preferably 30 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less.

"Laminate"
The laminated body of the present invention is obtained by laminating the third resin layer of the above-mentioned laminated sheet of the present invention adjacent to the base material.
3 and 4 show schematic cross-sectional views of the laminated body of the embodiment according to the present invention. The same components as those in FIGS. 1 and 2 are designated by the same reference numerals. In the figure, reference numerals 20X and 20Y are laminates, and reference numeral 21 is a base material.

The form of the base material is not particularly limited, and examples thereof include a substrate, a sheet, and an arbitrary form of a molded product. The material of the base material is not particularly limited, and examples thereof include glass, metal, ceramic, wood, paper, non-woven fabric, woven fabric, leather (artificial leather or natural leather), resin, and a combination thereof. The above-mentioned laminated sheet of the present invention can be laminated on various base materials and used as a skin material (surface protection sheet, design-imparting sheet, etc.) of the base material for the purpose of protecting the base material or imparting design. .. In addition, since the adhesiveness between the base material and the laminated sheet is good, it is preferable to perform the lamination so that the third resin layer is adjacent to the base material.

Examples of the resin used for the base material include a thermoplastic resin, a thermosetting resin, an energy ray curable resin, and a combination thereof. For example, polyesters, polyamides, polyimides, polyolefins, polystyrenes, styrene-methacrylic acid copolymers, acrylonitrile-styrene copolymers, polysulfones, polyurethanes, acrylic polymers, cellulose acetates, cellophane, vinyl chloride polymers, fluoropolymers. , And combinations thereof.

Glasses used for the base material include silicate glass, low iron glass, tempered glass (“Gorilla Glass®” manufactured by Corning Inc., and “Dragontrail®” manufactured by Asahi Glass Co., Ltd. Tempered glass, etc.), CeO-free tempered glass, float glass, colored glass, special glass (glass containing components that control sunlight or heat, etc.), coated glass (for the purpose of controlling sunlight or heat, etc.) Glass etc. whose surface is sputtered with a metal such as silver or a metal oxide such as indium tin oxide), low E glass, Saint-Gobin N. et al. A. Inc. (Trumbauersville, PA) "Toroglass (registered trademark)", PPG Industries (Pittsburgh, PA) "Solexia (registered trademark)", PPG Industries (registered trademark), and the like can be mentioned.

Examples of the metal used for the base material include iron, copper, aluminum, magnesium, nickel, chromium, zinc, and combinations thereof. The base material may be one in which the surface of a base material of any material is plated with metal such as copper plating, nickel plating, chrome plating, tin plating, zinc plating, platinum plating, gold plating, and silver plating.

Examples of the ceramic used as the base material include metal oxides, metal carbides, and metal nitrides. Specific examples thereof include cements, alumina, zirconia, zinc oxide-based ceramics, barium titanate, lead zirconate titanate, silicon carbide, silicon nitride, and ferrites.

Examples of the wood used as the base material include ovancol, bubinga, bird's eye maple, curly maple, white ash, sapele mahogany, tamo, sugi, cypress, cherry, and teak.

The method for producing the laminate is not particularly limited, and a method for multi-layer molding a base material (base material layer) made of another resin together with the first to third resin layers by the above method, the laminated sheet of the present invention can be directly obtained. , A method of heat roll laminating on a base material of an arbitrary material, a method of coating a laminated sheet of the present invention on a base material of an arbitrary material by extrusion laminating molding, and the like.

The surface of the base material on which the laminated sheet of the present invention is laminated may be subjected to a known surface treatment such as corona discharge treatment in advance in order to improve the adhesive strength.

The laminate of the present invention is, for example, a signboard component or marking film such as an advertising tower, a stand signboard, a sleeve signboard, a column signboard, and a roof signboard; a display component such as a showcase, a partition plate, and a store display; a fluorescent lamp cover, a mood. Lighting parts such as lighting covers, lamp shades, light ceilings, light walls, and chandeliers; Interior parts such as furniture, pendants, and mirrors; Exterior decorations such as doors, dome, and FRP; Safety windowpanes, partitions, staircase wainscots, etc. , Balcony wainscots, and building components such as roofs of leisure buildings; aircraft windshields, pilot visors, motorcycles, motorboat windshields, bus shading plates, automotive interior / exterior components (side visors, rear visors, head wings, headlights) Transporter-related parts such as covers, bumpers, sun roofs, and glazing); nameplates for audiovisual images, stereo covers, TV protective masks; medical equipment parts such as incubators and roentgen parts; machine covers, instrument covers, experimental equipment, rulers , Dials, and equipment-related parts such as observation windows; Optical-related parts such as liquid crystal protective plates, light guide plates, light guide films, frennel lenses, lenticular lenses, front plates of various displays, and diffuser plates; road signs, guide plates , Curved mirrors, and traffic-related parts such as soundproof walls; Others, greenhouses, large water tanks, box water tanks, bathroom parts, clock panels, bathtubs, sanitary, desk mats, game parts, toys, face protection masks during welding; , Mobile phones, furniture, vending machines, surface materials used for bathroom members, and the like.

As described above, the laminated sheet of the present invention contains a first resin layer containing a methacrylic resin (A), a second resin layer containing a phenoxy resin (B), and a second resin layer containing an ionomer (C). It is provided with 3 resin layers. Since the adhesiveness between the phenoxy resin (B) and the ionomer (C) is good, according to the present invention, the resin layer containing the methacrylic resin (A) and the resin layer containing the ionomer (C) are provided. , It is possible to provide a laminated sheet having excellent interlayer adhesiveness and adhesiveness to various base materials.
According to the present invention, it contains a resin layer containing a methacrylic resin (A) and a resin layer containing an ionomer (C), has excellent interlayer adhesiveness and adhesiveness to various substrates, and has high transparency. It is also possible to provide a laminated sheet having a high surface hardness.
Since the laminated sheet of the present invention has excellent adhesiveness between the second resin layer containing the phenoxy resin (B) and the third resin layer containing the ionomer (C), it is suitably manufactured by melt coextrusion or the like. be able to.
The laminated sheet of the present invention can be laminated on various base materials as a surface protection sheet, a design-imparting sheet, or the like, and can provide a laminated body having excellent adhesiveness between various base materials and the laminated sheet.

Hereinafter, production examples, examples, and comparative examples according to the present invention will be described.

[Evaluation items and evaluation methods]
The evaluation items and evaluation methods in the production examples, examples, and comparative examples are as follows.
(Weight average molecular weight (Mw))
The weight average molecular weight (Mw) of the resin was determined by the GPC method (gel permeation chromatography method). Tetrahydrofuran was used as the eluent. As a column, two TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and a SuperHZ4000 connected in series were used. As the GPC apparatus, HLC-8320 (product number) manufactured by Tosoh Corporation equipped with a differential refractive index detector (RI detector) was used. A sample solution was prepared by dissolving 4 mg of the resin to be measured in 5 ml of tetrahydrofuran. The temperature of the column oven was set to 40 ° C., the eluent flow rate was 0.35 ml / min, 20 μl of the sample solution was injected into the apparatus, and the chromatogram was measured. 10 points of standard polystyrene having a molecular weight in the range of 400 to 5000000 were measured by GPC, and a calibration curve showing the relationship between the retention time and the molecular weight was prepared. The Mw of the resin to be measured was determined based on this calibration curve.

(Glass transition temperature (Tg))
After drying 10 mg of the resin or the resin composition at 80 ° C. for 24 hours, the resin or the resin composition was placed in an aluminum pan. After performing nitrogen substitution for 30 minutes or more using a differential scanning calorimeter (“Q20” manufactured by TA Instruments), the temperature is raised from 25 ° C. to 200 ° C. at a rate of 20 ° C./min in a nitrogen stream of 10 ml / min. After holding at 200 ° C. for 10 minutes, the mixture was naturally cooled to 25 ° C. (primary scanning). Then, the temperature was raised to 200 ° C. again at a rate of 10 ° C./min (secondary scanning), and the glass transition temperature (Tg) was calculated by the midpoint method.

(Total light transmittance, haze)
For the single-layer sheet or the laminated sheet, the total light transmittance and haze were measured using a spectrocolorimeter (“SE5000” manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with JIS K 7361.

(surface hardness)
The surface pencil scratch hardness of the laminated sheet was measured using a table-movable pencil scratch tester (model P) (manufactured by Toyo Seiki Co., Ltd.). The evaluation surface in the case of the laminated sheet was the surface of the first layer shown in Table 3. Under the conditions of an angle of 45 degrees and a load of 750 g, the pencil core was pressed against the surface of the laminated sheet and scratched, and the presence or absence of scratches was confirmed. The hardness of the pencil lead gradually increased, and the hardness of the lead, which was one step softer than the time when the scar was generated, was used as the data of the pencil scratch hardness.

(Interlayer adhesive strength)
The 90 ° peel-off adhesive strength of the laminated sheet was measured according to JIS K 6854-1. The laminated sheet was cut into a size having a width of 15 mm and a length of 150 mm. The measurement was carried out in an environment of 23 ° C. and a relative humidity of 50% for a sample whose temperature and humidity were controlled for 24 hours in an environment of 23 ° C. and a relative humidity of 50%. Using a small tabletop tester ("EZ-SX" manufactured by SHIMADZU), measurement was performed under the condition of a tensile speed of 300 mm / min until peeling of at least 50 mm occurred, and the average peeling force was obtained from the obtained force-grasping movement distance curve. Was obtained, and the interlayer adhesive strength was evaluated. In addition, those in which at least one layer was broken before peeling, or those in which the interlayer adhesion was strong and the peeling test could not be performed were evaluated as "no peeling".

(Adhesion to substrate)
In the laminates obtained in Examples and Comparative Examples, the 180 ° peel-off adhesive strength between the base material and the laminated sheet was measured according to JIS K 6850. The test was carried out in an environment of 23 ° C. and a relative humidity of 50% for a laminate whose temperature and humidity were controlled for 24 hours in an environment of 23 ° C. and a relative humidity of 50%. A tensile shear adhesive strength test was carried out under the condition of a tensile speed of 50 mm / min using "Autograph AG-1S" manufactured by Shimadzu Corporation, and visually evaluated according to the following criteria.
<Evaluation criteria>
Good (○): Cohesive failure occurred at the adhesive interface (it can be judged that the adhesive strength is excellent).
Possible (Δ): Cohesive fracture occurred partially at the adhesive interface (it can be judged that the adhesive strength is relatively excellent).
Impossible (x): Peeling occurred at the adhesive interface (it can be judged that the adhesive strength is inferior).

[Methacrylic resin (A), Phenoxy resin (B)]
In Production Examples, Examples, and Comparative Examples, the methacrylic resin (A) and the phenoxy resin (B) shown below were used.
Methacrylic resin (A1): "Parapet" manufactured by Kuraray Co., Ltd.,
Phenoxy resin (B1): "JER1256" manufactured by Mitsubishi Chemical Corporation,
Phenoxy resin (B2): "YP50S" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
Table 1 shows the structure and physical characteristics of these resins. The total light transmittance and haze were evaluated for a 1 mm thick single-layer sheet obtained by putting a molten resin in a mold and press-molding it at 230 ° C. and 50 kg / cm ^{2 for} 5 minutes. Carried out.

[Ionomer (C)]
In Examples and Comparative Examples, ionomer (C1), which is an ion neutralizing derivative of a copolymer of α-olefin and α, β-unsaturated carboxylic acid or α, β-unsaturated dicarboxylic acid anhydride shown below. )It was used.
Ionomer (C1): Made by DuPont.

[Base material]
In the examples and comparative examples, the following base materials were used.
Glass: Float glass plate (manufactured by Nippon Sheet Glass Co., Ltd., thickness 5.0 mm),
Metal: Aluminum plate (5N material manufactured by Nippon Light Metal Co., Ltd., thickness 0.3 mm),
Ceramic: Cement board ("ASRock (registered trademark)" manufactured by NOZAWA CORPORATION, thickness 60 mm),
Wood: Natural wood veneer decorative plywood (manufactured by Hattori veneer, thickness 2.5 mm),
Polyolefin: Unstretched transparent polypropylene sheet ("Super Pure Array (registered trademark)" manufactured by Idemitsu Unitech Co., Ltd., thickness 0.4 mm).

[Manufacturing Examples 1 to 5]
The phenoxy resin (B1) or (B2) and the methacrylic resin (A1) are supplied to the hopper of the twin-screw extruder at the blending ratios shown in Table 2, melt-kneaded at a cylinder temperature of 230 ° C., extruded, and pelletized. Phenoxy resin compositions (R1) to (R5) in the form were obtained. Table 2 shows the structure and physical properties of these resin compositions. The total light transmittance and haze were determined for a 1 mm thick single-layer sheet obtained by placing a molten resin composition in a mold and press-molding it at 230 ° C. and 50 kg / cm ^{2 for} 5 minutes. Evaluation was carried out.

[Examples 1 to 7]
Pellets of methacrylic resin (A1) were continuously charged into a vent-type single-screw extruder having a shaft diameter of 50 mm, and melt-extruded under the conditions of a cylinder temperature of 190 to 230 ° C. and a discharge rate of 20 kg / hour. Peloxy resins (B1), (B2) and pellets of any of the phenoxy resin compositions (R1) to (R5) are continuously charged into a vent-type single-screw extruder having a shaft diameter of 30 mm, and the cylinder temperature is 190. It was melt-extruded under the conditions of ~ 230 ° C. and a discharge rate of 1 kg / hour. Pellets of ionomer (C1) were continuously charged into a single-screw extruder having a shaft diameter of 30 mm, and melt-extruded under the conditions of a cylinder temperature of 150 to 190 ° C. and a discharge rate of 9 kg / hour.
The melted methacrylic resin (A1), the phenoxy resin (B1), (B2), any of the phenoxy resin compositions (R1) to (R5), and the ionomer (C1) are introduced into the junction block. , Laminate extruded (coextruded) from a multi-manifold die with a width of 300 mm set at 230 ° C., and formed into a sheet by niping with an embossing roll set at 40 ° C. and a metal mirror surface roll set at 100 ° C. It was picked up at a speed of .55 m / min.
As described above, a first resin layer containing a methacrylic resin (thickness 2000 μm), a second resin layer containing a phenoxy resin (thickness 100 μm), and a third resin layer containing an ionomer (thickness 900 μm). ) And were sequentially laminated to obtain a coextruded laminated sheet (total thickness 3000 μm) having a three-layer structure. The nip was made so that the third resin layer side containing the ionomer was in contact with the embossed roll.
Separately, for various evaluations, a press-molded laminated sheet having the same three-layer structure produced by a press machine using a mirror-finished die was obtained.
The composition and evaluation results of each layer of the press-molded laminated sheet are shown in Tables 3 and 4.
Further, the obtained co-extruded laminated sheet (width 25 mm, length 100 mm) and the above-mentioned various base materials (width 25 mm, length 100 mm) are partially placed so that the third resin layer and the base material are adjacent to each other. The layers were placed in a mold frame and pressed at 230 ° C. and 50 kg / cm ² for 5 minutes to obtain a laminate having a width of 25 mm and a length of 175 mm. The width of the overlapped portion was 25 mm, and the length was 25 mm. Table 5 shows the evaluation results of the adhesiveness between the laminated sheet and various base materials.

[Comparative Examples 1 and 2]
Coextrusion molding lamination in the same manner as in Example 1 except that the structure is a two-layer structure of a first resin layer and a third resin layer or a two-layer structure of a first resin layer and a second resin layer. Sheets and press-molded laminated sheets were prepared and evaluated. The composition of each layer and the evaluation results are shown in Tables 3 and 4.
Further, in the same manner as in Example 1, a laminate of the obtained coextruded laminated sheet and various base materials was obtained and evaluated. Table 5 shows the evaluation results of the adhesiveness between the laminated sheet and various base materials.

[Summary of evaluation results]
In Examples 1 to 7, three layers of a first resin layer containing a methacrylic resin (A), a second resin layer containing a phenoxy resin (B), and a third resin layer containing an ionomer (C). A laminated sheet of structure was obtained.
The second resin layer containing the phenoxy resin (B) had good interlayer adhesiveness with the third resin layer containing the ionomer (C). As the content of the phenoxy resin (B) in the second resin layer increased, the interlayer adhesiveness with the third resin layer tended to improve. However, the Tg of the second resin layer tended to decrease as the content of the phenoxy resin (B) increased. By using the first resin layer containing the methacrylic resin (A) having a high Tg and a high surface hardness, the heat resistance and surface hardness of the laminated sheet can be increased, and when laminated on various substrates, it is softened and softened. Deterioration of the surface shape of the laminated sheet due to scratches was suppressed. Further, by adding the methacrylic resin (A) to the second resin layer, the heat resistance and hardness of the second resin layer could be increased. The second resin layer composed of the methacrylic resin (A) and the bisphenol A type phenoxy resin (B1) or (B2) had a total light transmittance of 90% or more and good transparency. The laminated sheets of Examples 1 to 8 had a total light transmittance of 90% or more and good transparency even in the entire sheet. The third resin layer containing the ionomer (C) had good adhesiveness to various substrates.

In Comparative Example 1 in which a laminated sheet having a two-layer structure of a first resin layer containing a methacrylic resin (A) and a third resin layer containing an ionomer (C) was obtained, the interlayer adhesiveness of the laminated sheets was poor. there were.
In Comparative Example 2 in which a laminated sheet having a two-layer structure of a first resin layer containing a methacrylic resin (A) and a second resin layer containing a phenoxy resin (B) was obtained, various substrates of the laminated sheet were used. The adhesiveness was poor.

The present invention is not limited to the above embodiments and examples, and the design can be appropriately changed as long as the gist of the present invention is not deviated.

This application claims priority on the basis of Japanese application Japanese Patent Application No. 2016-066027 filed on March 29, 2016, and incorporates all of its disclosures herein.

10X, 10Y Laminated Sheet 11 First Resin Layer 12 Second Resin Layer 13 Third Resin Layer 14 Other Resin Layers 20X, 20Y Laminated Body 21 Base Material

Claims (9)

A first resin layer containing a methacrylic resin, a second resin layer containing a phenoxy resin, and a third resin layer containing an ionomer are provided, and the second resin layer and the third resin layer Laminated sheets that are adjacent to each other. The laminated sheet according to claim 1, wherein the second resin layer further contains a methacrylic resin. The laminated sheet according to claim 2, wherein the second resin layer contains 50 to 99% by mass of the phenoxy resin and 50 to 1% by mass of the methacrylic resin. The laminated sheet according to any one of claims 1 to 3, wherein the phenoxy resin is a bisphenol A type phenoxy resin. The ionomer is any of claims 1 to 4, wherein the ionomer is an ion-neutralizing derivative of a copolymer of an α-olefin and an α, β-unsaturated carboxylic acid or an α, β-unsaturated dicarboxylic acid anhydride. Laminated sheet. The fifth aspect of claim 5, wherein the content of the monomer unit derived from the α, β-unsaturated carboxylic acid or the α, β-unsaturated dicarboxylic acid anhydride in the copolymer is 2 to 30% by mass. Laminated sheet. A laminated body in which the third resin layer of the laminated sheet according to any one of claims 1 to 6 is laminated adjacently on a base material. The laminate according to claim 7, wherein the base material contains glass, metal, ceramic, wood, paper, non-woven fabric, woven fabric, leather, or resin. The laminated sheet according to any one of claims 1 to 6, wherein at least two layers of the first resin layer, the second resin layer, and the third resin layer adjacent to each other are laminated by melt coextrusion. Manufacturing method.

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